Generally, when forming a dye-image with a silver halide photographic light-sensitive material, the silver halide photographic lightsensitive material (hereinafter simply referred to as a light-sensitive material) which comprises a support, provided thereupon, at least one silver halide emulsion layer containing a hydrophobic dye-forming coupler is, after imagewise exposing, treated with a color developer containing an aromatic primary amine as a color developing agent (hereinafter simply referred to as a color developing agent), then further treated with a bleacher as well as a fixer (or, with a bleach-fixer) to produce a dye-image.
In this case, it is widely known in the art that a blue-sensitive silver halide emulsion, a green-sensitive silver halide emulsion and a red-sensitive silver halide emulsion are used as siliver halide emulsions, and that couplers respectively forming a cyan dye-image, a magenta dye-image and a yellow dye-image are used as hydrophobic dye-forming couplers.
Recently, the strong need for light-sensitive materials capable of rapid processing has been mounting in the photographic art. In other words, lightsensitive materials are subjected to the running treatement with an automatic developing machine provided within every processing laboratory. It has been more and more strongly demanded that to improve the service for end users the development be finished within the same day, or, more seecifically, within one hour of acceptance of films to be developed.
In principle, in order to accelerate the development, each of the color developing process, bleaching process, fixing process or, bleach-fixing process as well as washing or stabilizing process must be independently accelerated. Among these processes, the acceleration of color developing process is, both in terms of photographical technology and practical use, of great significance. In order to accelerate color developing process, such means are most commonly employed as to raise the developing temperature, to raise the pH, to decrease the ion concentration of bromide which is the principal component of a developing inhibitor, to raise the concentration of color developing agent, or the like.
However, raising the temperature of color developer drastically accelerates the degradation of color developing agent due to oxidation by oxygen, therefore, is not suitable for continuous treatment in the long time span. Such a degradation becomes especially significant when the temperature is set greater than 40.degree. C. Similarily, when the pH of color developer is raised, the coupling reaction of the oxidized product of the color developing agent and the coupler unexpectedly becomes impossible at a certain pH level. Especially, the pH of more than 11, therefore, it is impossible to raise indefinitely the pH of the color developer.
At the same time, a color developer often contains benzyl alcohol as a color forming accelerator. When such a benzyl alcohol is incorporated into the color developer, a dye-image featuring a higher maximum density and gradation can be obtained. More specifically, to obtain the satisfactory color forming properties when treating a color photographic light-sensitive material through color developing with a color developer containing benzyl alcohol, usually 10 ml to 15 ml or more of such a benzyl alcohol is incorporated into 1 liter color developer. However, because the benzyl alcohol has a poor watersolubility, it is normally necessary to add as an auxiliary solvent a considerable amount of multivalent alcohol such as ethylene glycol, diethylene glycol, triethylene glycol, glycerin or the like, in order to solubilize benzyl alcohol.
However, since such multivalent alcohols and benzyl alcohols have the greater pollution loads including BOD (biochemical oxygen demand) and COD (chemical oxygen demand), it is desirable in view of the environmental pollution to minimize or to totally eliminate the use of these substances.
Incidentally, it has been more strongly demanded recently that the photographic light-sensitive material, comprising a reflective support being typified by a color photographic paper, can provide a dye-image featuring a great fastness.
In view of such a feature, especially in terms of the light fastness of a dye image, the methods to select a coupler featuring a smaller discoloration and color-fading, to use an ultraviolet-ray absorvent for protection of dye-image against ultraviolet-rays or to use a anti-fading agent for prevention of fading due to light have been conventionally proposed.
For instance, the method for improving the light fastness of a dye-image by incorporating and blending an ultraviolet-ray absorvent into a color photographic material significantly improves the light fastness of a dye-image, when compared to the case where no ultraviolet-ray absorvent is incorporated. However, such a method has a disadvantage that the dye-image is stained due to the coloring of the ultraviolet-ray absorbent itself when such an amount of the absorbent as to provide satisfactory effect is used. Additionally, despite its use, the ultraviolet-ray absorbent has no preventive effect against the fading of dye-image due to the visible ray, thus limiting the improving effect on the light fastness by means of the ultraviolet-ray absorbent.
In the meantime, the examples of an anti-fading agent which prevents the fading due to light are as follows: bisphenols disclosed in Japanese Patent Examined Publications No. 31256/1973 and No. 31625/1973; pyrogallols and gallic acid and esters thereof disclosed in U.S. Pat. No. 3,069,262; alpha-tocopherol and acyl derivatives thereof disclosed in U.S. Pat. No. 2,360,290 and Japanese Patent Publication Open to Public Inspection hereinafter referred to as Japanese Patent O.P.I. Publication No. 27333/1976; 6-hydroxychromans disclosed in U.S. Pat. Nos. 3,432,300 and No. 3,574,627; 5-hydroxychroman derivatives disclosed in U.S. Pat. No. 3,573,050; 6,6'-dihydroxy-2,2'-bisspirochromans disclosed in Japanese Patent Examined Publication No. 20977/1974; organic metal-chelate compounds disclosed in U.S. Pat. No. 4,050,938, Japanese Patent O.P.I. Publications No. 62826/1979, No. 62987/1979, No. 82385/1979 and No. 82386/1979; 6,6'-dihydroxy-2,2'-bisspirochromandialkylethers disclosed in Japanese Patent Examined Publication No. 19765/1982; hydroquinonedialkylethers disclosed in Japanese Patent Examined Publication No. 24257/1981; compounds having sterically hindered phenol group and disclosed in Japanese Patent O.P.I. Publications No. 48535/1979 and No. 222853/1985; polyalkylpiperidine compounds disclosed in Japanese Patent Examined Publication No. 20617/1982, Japanese Patent O.P.I. Publications No. 114036/1983, No. 119351/1984 and No. 116747/1984.
Among these dye-image stabilizers, the above-mentioned compounds having sterically hindered phenol group as well as polyalkylpiperidine compounds are, as light stabilizers for yellow-dye-image and cyandye-image, favorably used. In other words, the compounds having sterically hindered phenol group as well as the polyalkylpiperidine compounds can improve the light fastness of a dy--image, without jeopardizing the dark-storability, or without causing the undesirable discoloration (stain) due to light, heat and moisture.
However, it was learned that the color forming properties are disadvantageously degraded, resulting in a deteriorated gradation and a decreased maximum density, when the light stabilization effect of such a compound having sterically hindered phenol group (hereinafter referred to as HP) as well as a polyalkylpiperidine series compound (hereinafter, PAP) are enhanced to the sufficient point.
Such a disadvantage is especially significant when benzyl alcohol contained in the color developer is eliminated from the color developer.
More surprisingly, it was learned that the light fastness of cyan- and yellow-dye-images obtained under such conditions of color developing with such deteriorated color forming properties is sometimes poorer than that obtained through the treatment with a color developer containing benzyl alcohol, and that in some cases the light fastness of dye-image obtained by treating the lightsensitive material containing the above-mentioned HP or PAP with a color developer containing no benzyl alcohol is poorer than the similar fastness of dye-image obtainable by treating the lightsensitive material containing no HP or PAP with a color developer containing benzyl alcohol.
The inventors have found through the devoted research that the deterioration in light fastness of dye image obtained by the treatment with the color developer containing no benzyl alcohol is caused by the use of hydroxylamine salt being contained in the color developer.
The above-mentioned hydroxylamine is an excellent preservative being contained in an ordinary color developer especially when it is used together with sulfurous ions, and is available at a lower price. Additionally, the hydroxylamine exerts only a minimal influence on benzyl alcohol.